Thomas m



Patented June 11, 1929.

ma'mg bbtpms, or SANDWIC itrass'aoHusn'ris; mom in.

' 'rna'ronbr SAID JOHN ncoL'Lms, nncnasnn.

wa on "oomrosrrr'oitormrsr'rnn r03 nominee Aim rnocnss ornaxme an No'Drawin g'H W V This invention relatesito improvements in compositions of: matteri for moldingandin theiprocessiof-making-theisame.

: A More; particularly it relates to the ingred1-;

5: ents whichare to-be ecnnbi ned,- and themeth 0d of combining; them= for ithe. preparation.

of materials: which can; be-used in. :plastic form asfor .the manufacture of articles whose shape is determined by molding:un-. der .heat and; pressure, and. for other uses. Onelarge field withwhich the utilities of theinvention .are identified: is that in which the product known commercially as bakelite is so extensively used.-. It.is one.object of-the 15. present invention .to provide materials andmethods 1 less expensive than those of bake-- litezfonproducing results .which can serve: many aor, all of the .commercial purposes for which bakelite is used. ltiisanother-object- =.t0 accomplislnyt-his' .vwithout..resort to the phenol-formaldehyde condensation process which. is characteristic of the :bakelite manu-' facture, Another. and.\-'er.y.zimportant objectisto provide aprofitable market for materials ,which at presentiare. considered as waste and are so treated, to wit,-the black liquor. resultingin the: digestion of wood in the soda. process and in the sulfate process, of makingpulp. from wood, Whereas it is customary in the manufacture of commercial products knownas bakelite and others of like utility, to introduce a filler or me-- chanical carrier or binder ofother materials such .as ground wood, or sheets of paper which are impregnated with the active material, it is a purpose of the present invention to improve upon that phase of the bakelite process and cognate processes by the introduction of a binding agent which is of a fi-- brous nature and notable for its strength; and the introduction of this by a method which is simple, etfective, and free from labor costs and costs for time and for machinery operation hitherto practiced, or at least in which-the costs chargeable to the preparation of the binder are very much reduced below those heretofore known. In another aspect the invention amounts to the conversion of suitable woods, as for example, coniferous woods, which are likely to afford the greatest field for utility of the invention. into articles of plate or molded form, which are harm-smooth, strong. not readily subject to disintegration by any means, and capable of -Appllcation filed Iu1y31; 1926. Serial No. 126,344.

indefinite duration, having also gooddielec-:

trio properties, insoluble and infusible. These objects are accomplished by the d-i-i gesting of the wood as is alreadycustomary in the soda .or sulfate process,- thus, separat-- pulp or cellulosic, --material ing it into its and HOB-108111110810 material throwing down; a precipitate from the latter'by adding acid;- beatinggthe pulp andthe precipitate thonoughly. together. This makes athiekpasty:

massifromiwhich liquid can. beremoved by as pressure againstea screen, and which when dry can .be molded ,underheat andi pressure to 'desired commercial form. =-=The produet obtained by precipitation front-the black liquor,. and; resm acids, can be handled -in mo1st' form for mixture with the moist-pulp. The pulp having first been sizedwith rosin, after the manner practiced by paper manuhich s-thought to be largely lignin facturers in a beating engine, the precipi 7 tate eanbe added and the mixing continued inzthe same-beatingengine until the product is ready tobe dried and molded. -In the mold, anapplication of pressure of two-to three thousand. pounds per square inch at a temperature of three to four hundred degrees Fahrenheit, for a half an -hour to 'anhour produces the final durable product. The. importance of the simultaneous=fibredrawing, coating and intimate-mixing step 8 then appears, for whereas the precipitate by itself had. a vitreous fracture and but little strength, the final composition has a diminished and reluctant fracture, and can withstand greater preliminary stress and 9 preliminary strain.

The materials and process described are also of value in connection witht-he typical baltelite process. In this case cresylic acid may be used for making the precipitate, and 9 formaldehyde may be added and preliminarily mixed with the precipitated powder before the same is put into the beater with the pulp, and the rosin size would not be used on the pulp. The phenol and formalde- 1 hyde condensation product resulting from heat and pressure would then be intermingled with the other lash-rials in the com osition. the whole being hound thoroug ly together. 1 In either event the product can be provided with a veneer facing by pressing a substance on the face of the mass in the mold,

so as to give it the desired color or surface aspect according to methods already well known.

For an illustrative example one may consider the makings ot' a thin hard board suitableior radio or electrical work. The digesting: action having been completed in the soda process for the iiianut'acture of pulp, the liquid with pulp floating in it is custmnariiy blown from the digester into a wash tank harinp a screen bottom. The black liquor having been drained away, the pulp thus separated by the screen, after beinc washed with water to carry out all remtiining alkali, is ready for its ordinary use in paper making, or according to the present invention for recombination with .a derivative of the black liquor, In order to make the ssn bination in d sired prnper= tuins, while using thspul in wet term, the net amount at pul 1n t s Wet mass is t be ascertained. is is done by findin h w mu h bone dry pulp rssult trnin the dry ng of it known quantity of the wet nip inths in e at wetness inwhich it is a he u ed, Lirwisc the precipitate train the black liquor may be used in wsttorm The u ce ful practice of- .the invention does. not require that there be any recise and exact relati n f uiintity of to quantitv of the pre -ini iate derived rain the black l quor, but it will ordin iril be des red for comm rc al rea ns to put them ogether in ome s settled proportion It is her-ii inn d or p rp e of illu t ation that th y are to be combined in equal part A uitable ratio is four pounds cash of dry pulp and of pr cipitate with t n gal ons otwiitsri and. re in size to th ex ent de ired, the amount required being materially less than equal parts with the pulp and pre ipitate, s-

about 1971 of th pulp;

h precipitate i obtained a fnlluw Add two pound of i niiiinur iiil ulfuric acid to t n callou of hliicli iqu r or u irliiitsrrr inuuuit of acid is ii tiihls iii:- rordii to he ii'riiuth ot the hlir'h lil i uri l lli tirriiu, ii precipitate quickly t uet 'ii l itl ir ti'aiurd out hr putting the whole ii i'iitliiii shrrii iu' through hi h ii uhu'lr liiiuid p 'lh pr ripitatu iii i lipiii ril i ul ii u nil-Y tliilit [h h' i i i i iiihi iirs the i i if illlli i r ii i iiii iits iii the uriui l u'ooii. iu hidiua c lll 'il i and ii t r i t ruii t Hill funds the ri riiiiis resinous si hsia rns which characterize [hii i irrcater decree than u h i' u'uad i all at u'h h hare h th rto al urt wa te in th hi ch liu iuiz Th precipitate pi'ei ii l ly may he purified by wii hiiiu it i 'iit i' in li'llti Yii Willi-l s iuhl'r solids and all substances that i'-lll h lilll sml n i ll hi ziiltilliliii liiililil :ill i iili 'i i iii gut l-ili of other impiiriiii.-, and tin-n liiili cipitated by adding acid. In commercial practice it will be advisable to set apart a measured quantity of each batch of black liquor precipitate in either its crude or purified form, according to the plan which is to be followed, and thus to determine the net value of the wet stock in terms of dry precipitate content. This having been ascertained the quantity can be computed to know in what proportions to combine wet precipitate with the wet pulp.

The putting together of the ingredients may begin with the beating together of the pulp and the resin size, such as is used in the manufacture of paper, in a beating enqine of the kind that:- is used in a paper mill. The entire estimated quantity of water having been added to the pulp the resin size is preferably to be mixed and beaten with it until it can he seen that the pulp is flier: iighly covered with the rosin, making quite a hasty viscous liquid. The precipitate may then he added, with further beating until there is a uniform mixture. The time re quired for the heating is not long, and ordinarily in a small engine twenty minutes or less is nnuirh in each case. The produia which is a thick pasty mass can be put into a, screen mold and there pressed against the screen to extrude liquid. When dried it constitutes a light, thick, friable, obviously fibrous sheet which is available for various use that to which reference is here made being its capability of being molded under heat and pressure t s me desired i-(iiiiiiierend product. For example, to make a hard thin h ard or panel for radio or electrical u e the heet may be ressed between two highly polished plates. at a pressure of two thou and to three thousand pounds. and at i t mperature varying from three. hundred to f ur hiindrrd decrees l ahrruhrlt for train one halt an hour to an hour, The re= uit i ll smooth hard strong ubstance which o far as my t ts hare gene, ha su h duruhililr and oth r rualiiir as ar likely to i iiilui it very uetiii iu ihr arts, It appears lik ly that in the dr erihed iu ldiua'uprru= tiiu l chuiiiical reaction iii-curs, 'l n produrl i ii till, hard. trong phil 'i tough, hut oapahl of hriuc' rut 'lihu hiiiie or Hill; ii uhlc in r eiving in the mold a iuuuih, al y surfa e, and of retaining ii. uuall'erh rd hr humidity or liquid water. and non: arning; lowly uihu iihlr when laid on u l il iii coal but not lusihlr; and po essed oi dielectric properties,

'lhu color can he varied by die or pililiicii iii ii i hr i'r the hi uvi' l i lie The surface may he \i-iici'red hi i lhliiii'; w d r oth r th n h et on th hire ii the um lu'liiir the liit illiliij iiii-suii'e is applied, ii \i'hirh ill-i'- the veneer will iiilhi-ru il llllll'i i,

'Ihu ..-llii li|lii'i' may hr mold-d into \uriniii hrvuiu lltl Ilfi

itl l desired forms, and affords an inexpensive. convenient and durable product.

Itwill be understood that other varieties of pulp may be used for mixture with the black liquor precipitate, or materials other than pulp, for the function of this is that of a filler and binder. The length and strength of the pulp fibresdcrcloped in the treatment of coniferous woods by the soda process, coupled with the. commercial advantage of having them already at hand at the locus where the liquor is produced without freight charges being applicable to either, makes it advantageous to use this variety of pulp, and makes in the result a conversion of the wood into the product described.

In the material which is thus molded the active material is the precipitate from the black liquor, which has a resinous aspect so that it may be commonlyreferred to as a wood gum. This is fusible, and under hcat can be molded, but its molded product is not as strong as when a fibrous binder has been mixed with it; nor is the product of molding it at a low temperature or the product obtained by pouring and casting it. equal to the product of molding at the high temperature and pressure stated, for the former are re-moldable under heat, while the. latter appears to be fixed and seems not to yield to the application of a degree of heat equal to that under which it was formed. For commercial purposes, the gum may be sold as an article of commerce and transported in wet or dry condition. Drying may be accomplished by setting itout for sun drying or by evaporation in any dry room orby vacuum.

The wood gum may be used with advantage in connection with phenolic bodies and formaldehyde. For these purposes ordinary crude cresylic acid and formaldehyde may be prelnnlnarily mixed with the wood gum in its powdered form before it is put -into the beater with the pulp, and the rosin size applied to the pulp may be omitted. By the application of heat and pressure according to methods already known a product. resembling bakelite is obtained; but this has the fibrous pulp element throughout its sub- ..stance and also has the product of the wood gum. Underthese circumstances it is aproduct so like that of the wood gum alone, without any bakelite or bakelite ingredients. that I am not able to say with exact certainty just what the composition is; but it would seem that if bakelitc is formed a a condensation product of the phenol and formaldehyde. this condensation product as! 4 as a binder for the other material. white it it is not formed it is because the fUIlllltliiO- hyde has reacted with the black liquor or its precipitate, giving it the pro iierty of setting quickly in the mold while the cresylic acid reacts with the gum making a compound that has good flowing properties or plasticity in the mold. If these ingredients are to be used they may also be applied by heating theblack liquor, or the purified solution of its precipitate in caustic soda, with formaldehyde in the proportion of two parts of formaldehyde to one part of dissolved wood gum and obtaining an initial condensation, and then adding eresylic acid and heating again, the amount added being equal to the weight of the wood gum. Upon this acidification a precipitate separates which may be filteredand dried or may be compounded wet with pulp or other fibrous binder, giving a'mixture which molds well and will set quickly underheat and pressure. In this .variety of the process when the formaldehyde isadded to the black liquor the solution may be heated up to near the boiling oint of water and allowed to stand overnight. The odor of the formaldehyde disappears and this derived form of the gum when precipitated and molded has the property of setting quickly in the mold, so that there is reason to think that a separate compound is formed which is not identifiable with those produced under the processes known by the name of bakelite. But whatever may be the full explanation of the reaction it is evident that the wood gum or precipitate obtained from the black liquor plays an important part in contributing both bulk and properties of plasticity and tensile strength as does also the fibrous cellulosic ingredient with which it is thoroughly intermingled.

It thus has been shown that more than one derivative of black liquor may be used. The simplest derivative is the precipitate obtained by adding acid. and next to that the said purified form of the same; but an illustration has been given of a gum derived from a precipitate by chemical reaction; and any of these or others of the same type may effectively be utilized with fibrous material beaten, drawn and mixed together in pulpy stage by the close-set knives of a beating engine. The term derivative as used in the claim is therefore not restricted to the primary derivative. obtained directly by acidification of the black liquor. Other resinous materials may be handled by the process. In the case of applying the beating engine with phenol and formaldehyde the action must be watched carefully and stopped before the mixture gets too stitf, as occurs by the beginning of reaction. \Vhen merely making a. mechanical mixture of the precipitated gum and pulp the mixing can bc carrier much further; and the reduction of pulp to elemental masses of fibres is preterably accomplished only to such extent as does not result in cutting the fibres less than their natural length. In the dried product lOO of the mixture the aspect is distinctly that of a fibrous body; and such a sheet having for example three-fourths of an inch of thickness may be converted by simply heat and pressure to a sheet having say an eighth of an inch thickness which is neither pliable nor possessed of any fibrous as ect. In the case of treatment of a sheet by eat and pressure this is for the purpose hereof treated as being a molding of the material.

I claim as my invention:

1. A composition adapted to be transformed into a hard,-molded substance by heat and pressure, comprising a mass of finely separated fibres throughout which mass there is distributed a gummy derivative of black liquor.

2. A composition adapted to be transformed into a hard, molded substance by heat and pressure, comprising a fibrous mass of cellulosic material in which the fibres are finely separated from each other and loosely adhering together, and intimately intermingled with a gummy derivative of black liquor.

3. A composition adapted to be trans formed into a hard, molded substance by heat and pressure, comprising a mixture of a gummy derivative of black liquor and a finely divided wood product.

4. A composition adapted to be transformed into a hard, molded substance by heat and pressure, comprising a body of cellulosic material finely separated into fibrous elemental masses which are individually coated with a gummy derivative of black liquor.

5. A composition adapted to be transformed into a hard, molded substance by heat and pressure, comprising a mixture of a gum precipitated from black liquor and a finely separated fibrous mass of cellulosic material in which the fibres retain approximately their natural lengths.

6. A composition adapted to be transformed into a hard, molded substance by heat and pressure, comprising a mixture containing as ingredients a gum precipitated from black liquor and a finely divided fibrous substance.

7. A composition adapted to be transformed into a hard, molded substance by heat and pressure, comprising a mechanical mixture of a gum precipitated from black liquor and other substances which, independently of the gum, are capable by mutual reaction of making a hard, molded product.

8. A composition adapted to be transformed into a hard, molded substance by heat and pressure, comprising a mixture of a gum precipitated from black liquor and a partial condensation product of phenol and formaldehyde.

9. An intermediate product adapted to be converted by heat and pressure to a dense,

hard, molded final product comprising a mass resulting from the intimate mechanical mixture of a finely divided gummy precipitate from black liquor with pulp which has been produced from wood by the process in which the black liquor is produced.

10. An intermediate product adapted to been produced from wood by the process in which the black liquor is produced.

12. A composition of matter, being a dense and hard final product, eonn rising a dcrivative of a mixture ot a finely divided fibrous substance with a gummy precipitate of black liquor.

13. A preliminary process for making a molded product comprising the mixing together of a fibrous substance and a gummy derivative of black liquor, meanwhile subjecting the aggregate to drawing forces between close set mechanically moving elements which by friction and abrasion subdivide the fibrous masses finely and coat them with the gum.

14. A preliminary process for making a molded product comprising the intimate mechanical mixing of a finely divided gum precipitate from black liquor with a finely divided fibrous substance; and then forming the mixture into a mass throughout which both ingredients are uniformly distriluued; the said mass being an intermediate product adapted to be converted by heat and pressure to a dense, hard, molded, final product.

15. A process for making a molded product comprising the preliminary forming of a. light, thick porous, dry sheet throughout the whole of which there are distribut d afibrous substance and a gunnny derirutive from black liquor; and then subjecting the mixture to the action of heat and pressure by which the gum becomes fluid, and the fibres greatly compressed together in a thin sheet, followed by cooling. so that the gum solidifies and holds the fibres thus compressed, and the fibres strengthen the gummy structure.

16. A process for making a molded product comprising the intimate mechanical mixing in swatcr of a finelydivided gummy dcrirative of black liquor with a finely di vided fibrous substance; spreading the mixture while wet and drying it; heating and compressing the mixture to final form; and cooling the whole in final form, whereby a hard mass results, tree from fibrous aspect.

17. A process for making a molded product comprising the making of pulp and black liquor Ly cooking process, and separating the black liquor from the pulp; adding acid to the black liquor and obtaining a precipitate; separating the precipitate; mixing the precipitate and the pulp together wet; drying the mixture; and applying heat and pressure to the mixture to make a tough, hard molded product.

18. A process for making a molded product comprising the making of pulp and black liquor by cooking process; obtaining a precipitate from the black liquor by adding acid; mixing the pulp and precipitate and separating the liquid; drying the mixture; and applying heat and pressure to the mixture.

19. An intermediate product, comprising a light, friable mass of fibrous aspect embodying an intimate mechanical mixture of a fibrous substance with a gummy derivative of black liquor, and capable of being converted into a dense, hard and tough mass having resinous rather than fibrous aspect.

Signed at Boston, Massachusetts, this sixteenth day of February, 1926.

JOHN T. COLLINS. 

